自催化氧化添加PhBr到Pd(PtBu3) 2通过Pd(PtBu3) 2 ((H) ((Br) 通过Pd(PtBu3) 2
Fabiola Barrios-Landeros1, Brad P Carrow, John F Hartwig
1Department of Chemistry, University of Illinois, 600 South Mathews Avenue, Urbana, Illinois 61801, USA.
二与二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二三二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二 二) 化物种 (PtBu3) 2Pd (H) (Br) 作为催化剂,与甲相反应的速度比二) 前体更快.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 反应机制 反应机制
背景情况:
- 催化氧化添加是有机合成中的一个基本转变.
- 了解反应机制对于催化剂设计和优化至关重要.
- 自催化,即反应产物催化反应,是一个有趣的现象.
研究的目的:
- 阐明二与二三丁二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二三二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二
- 为了确定这种介导反应中的活性催化物种.
- 研究添加剂和反应中间体的作用.
主要方法:
- 涉及不同度的反应剂和添加剂的动力学研究.
- 使用光谱技术分析反应产物和中间体.
- 对不同类型的拉与甲相比较的反应性研究.
主要成果:
- 氧化添加通过一种不寻常的自催化机制进行.
- 确定了 (II) 化物复合物 (PtBu3) 2Pd (H) (Br) 作为活性催化剂.
- 甲与Pd(II) 催化剂的反应明显快于与Pd(0) 前体的反应.
结论:
- 提出了一种催化循环,包括从Pd(0) 种和P(tBu) 3·HBr中形成 (PtBu3) 2Pd(H) ((Br).
- 然后,Pd(II) 化物与甲烯反应,可能是通过一种阳离子中间体,以促进氧化添加.
- 最初的氧化添加产品的热分解有助于形成活性Pd (II) 催化剂.
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